Detergent-germicide composition



United States Patent DETERGENT-GERMICIDE COMPOSITION Lawrence L. Little Gilmore Qhen, Morris lains, N. J., assignors to E. F. Drew 8: Co. Inc., New York, N. Y., a corporation of Delaware No Drawing. Application July 8, 1950, Serial No. 172,777

9 Claims. (Cl. 252106) The present invention is directed to germicidal compositions, more particularly to combinations of germicides with detergents and particularly adapted for use in the food industries.

It has been known for some time that quaternary ammonium compounds having germicidal properties are effective against certain pathogenic bacteria. However, such compounds have been found ineffective for many applications because of the presence in natural waters of small amounts of compounds of ferric iron, calcium, magnesium and the like which seem to inactivate the germicide. It has also been found that such germicides are less effective against Gram negative bacteria than against Gram positive bacteria, which has greatly limited the usefulness thereof. Attempts have been made to overcome these difiiculties by adding to a solution containing such germicides an alkaline salt in sufficient quantity to raise the pH above 9.0. However, this caused an undesirable result in that the calcium and magnesium ions formed an objectionable precipitate. In an attempt to prevent such precipitation, a small amount of a polyphosphate was added but this had a further disadvantage in that such addition caused the precipitation of the germicide itself. In certain compositions tetra sodium pyrophosphate was used to prevent precipitation of the calcium and magnesium compounds but it was relatively ineifective although it did minimize to a certain extent the precipitation of the germicide.

There were other disadvantages in the use of said quaternary ammonium germicides together with detergents in the sanitizing of food processing machinery in that a relatively large amount of the germicide was necessary in order to give adequate germicidal action. Because of the expense of such germicides, it became commercially impossible to use in many cases. Also, this type of germicide acts as an anti-detergent agent, causing flocculation of the dirt and counteracting the detergent action of the various detergents used. Also, these germicides were relatively ineffective against the Gram negative bacteria.

The present invention is intended and adapted to overcome the difliculties and disadvantages inherent in compositions of the type described, it being among the objects of the present invention to provide a quaternary ammonium germicidal and detergent composition wherein the activity of the germicide is substantially increased.

It is also among the objects of the present invention to provide a composition of the type described, which is highly effective against Gram negative as Well as Gram positive bacteria.

It is further among the objects of the present invention to provide a composition having increased detergency and having a high degree of water softening effects.

It is still further among the objects of the present invention to provide a composition which may be used to clean and sanitize food processing machinery to combat pathogenic organisms, and which is highly economical in such use.

It has now been discovered by extensive experimentace v tion that quaternary ammonium germicides may be activated so that their potency is increased from two to five times its previous value. This is accomplished by providing an environment in the form of other chemical substances so that the germicide becomes relatively insensitive to the salts in the water used. As a result, the germicides become equally effective against the Gram negative bacteria and they may be used at a much lower concentration than previously, greatly decreasing the cost of the composition. The invention also lowers the concentration of the germicide, which minimizes and substantially eliminates the anti-detergent action of the cation of the germicides.

In practicing the present invention, it has been found that an ideal ionic environment is provided by introducing into the composition containing said germicide, a mixture of an alkali metal carbonate and an alkali metal polyphosphate. The ratio of said two constituents is 1 part of the alkali metal carbonate to 2-7 parts of the polyphosphate. Within these ratios it has been found that excellent results are obtained by utilizing a ratio of 1 part of said carbonate to 4-5.5 parts by weight of the polyphosphate. Optimum results may be obtained when certain of the higher polyphosphates are used, namely, those containing at least 3 atoms of phosphorus in the molecule. The amount of the quaternary ammonium germicide used in the compositions is preferably from 1% to 8% of the complete composition.

The germicide is one which has been known for a number of years and has been found effective for medicinal purposes, and having the following structural formula.

Percent by weight Quaternary'NHt Compound 1- 8 Alkali metal polyphosphate 20-75 Alkali metal carbonate 1025 Non-ionic wetting agent 1-10 The presence of a non-ionic wetting agent has been found to be highly advantageous in promoting the detergent effect of the composition Without interfering with the germicidal value thereof. There may be added to the composition substantial amounts of other detergent salts of inorganic acids. From 1% to 50% of such added salts may be used, thereby giving a better detergency or a higher pH for a particular purpose. The wetting agents may be of various types but must be non-ionic or cationic in character. Among such compounds are the polyalkylene glycol ethers and esters thereof, as Well as condensation products of alkylolamines and higher fatty acids.

The following are specific examples of compositions made in accordance with the present invention:

Example 1 The following composition was made:

Percent Sodium tripolyphosphate Sodium carbonate 15 Polyethyleneglycol ether 4 Quaternary NH4 germicide (50% B20) 6 This composition has been found highly effective for concentration of 3% in water.

general detergency in the care of food processing machinery.

This composition has proven highly effective in the care of food processing machinery which is hard to clean.

Example 3 A comparative test was made between applicants composition and aprior art composition in order to determine the relative effectiveness thereof. The prior art composition had the following formula:

Percent Sodium metasilicate 3O Tetrasodium pyrophosphate 55 Quaternary NH4 germicide 10 Polyethyleneglycol ether 5 Applicants formula was that given in Example 1. The compositions were tested under identical conditions against E. call, with the following results:

It will be noted that using applicants formula in various types of water, from distilled water to hard water,

there was no survival of bacteria. On the other hand, with the prior art formula, in hard water there was a very :large growth of bacteria. When the two types of com- ;positions were tested in skim milk, applicants formula showed a very modest growth of bacteria, but only in the hard water. On the other hand the prior art formula showed a growth of bacteria even in distilled water and in'waterof low hardness, permitting a substantial growth of bacteria, and the harder the water the moreprolific was the growth so that in the moderate and hard waters -the'bacteria were too numerous to count. In the compositions the same germicide was used and the same wetting agent. The germicide in both compositions was in a The number of bacteria listed in the table are per cc. 7

The various non-ionic wetting agents include the fatty acid esters or others of higher polyalcohols such as the alkylene glycols having 2 to 4 carbon atoms in each alkylene group. The molecular weight of the polyalcohols is at least 200 and preferably 400 or more. The fatty acids combined in the compositions have from 12 to 22 carbon atoms. The non-ionic condensation prod nets are made with fatty acids having from 12 to 22 carbon atoms and with alkylolarnines in which the alkyl group contains from 2 to 4-carbon atoms. The alkylolamine contains 2 or 3 alkyl groups and the ratio of fatty of said amine.

namely, those withstanding high temperatures.

The following are specific examples of the quaternary ammonium compounds suitable for the purpose:

Di-isobutyl phenoxy ethoxy ethyl dimethyl monium chloride Dodecyl dimethyl benzyl ammonium chloride (50% aqueous solution) Dodecyl benzene trimethyl ammonium chloride (50% aqueous solution) The following examples illustrate the wetting agents which may be employed in the present compositions:

benzyl am- Polyglycol ether Cal-I5 (CH2 9OCH2CH2OCH2CH2OCH2CH2OCH2CH2OH Ninol type detergent (fatty acid-amino condensate) C11H23CON(C2H4OH)2 Polyethylene glycol monolaurate In the presence of the ionic media in the above compositions, a product containing 2 to 4% of the quaternary ammonium germicide and used at a concentration of 0.30% in aqueous solution provides solutions containing 60 to p. p. m. of said germicide. Such solutions give superior germicidal action than those compositions con= taining to 200 p. p. m. but without the ionic media of the present invention. Furthermore, the detergency and water softening properties of the new compositions are distinctly superior to those of prior types of compositions, and the superiority is evidenced by the absence of scale, scum and film on'the articles cleaned thereby.

The present compositions are eminently suitable for use on dairy farms for treatment of utensils and equipment. They are effective not only against gram positive but also particularly against gram negative bacteria. They are effective in combatting thermoduric organisms, They are suitable for use in plants which process dairy products in the control of all types of bacterial contamination, especially E. coli and other Gram negative types. They are useful in canneries and other food processing plants in controlling the flat sour type of spoilage caused by thermophyllic and by spore forming bacteria, such as B. subtilis.

Although the invention has been described setting forth several specific-embodiments thereof, the inventionis not limited thereto as they were inserted for the purpose of illustration of the character of the invention. Various changes in the details may be made within the scope thereof. For instance, the compositions may be used under other conditions of temperature and concentration than described above. The ratio of the constituents may be altered and equivalent materials may be substituted in whole or in part. To the compositions may be added other substances which do not interfere with the functioningthereof; The trisodium phosphate maybe replacedin whole or in part by sodium metasilicate, boraz, or other alkaline detergents; monoor dialkali metal phosphates maybe used. The sodium carbonate may be formed in the final solution and may be replacedin the composition 'by equivalent amounts of mixtures of such substances as alkali metal silicates and bicarbonates which react to give the carbonates.

Theseand other changes may be;rnad e in the details without departing from thespirit of the invention, which is to be broadly construed and not to be limited except by thecharacter ofthe claims appendedhereto.

We claim:

1. A detergent-germicide composition consisting of a quaternary ammonium germicide, an alkali metal carbonate and an alkali metal polyphosphate taken from the class consisting of alkali metal triphosphates and tetraphosphates, the ratio of carbonate to polyphosphate being 1 to 4-5.5.

2. A detergent-germicide composition consisting of a quaternary ammonium germicide, an alkali metal carbonate and an alkali metal polyphosphate taken from the class consisting of alkali metal triphosphates and tetraphosphates, the ratio of carbonate to polyphosphate being 1 to 27, the amount of said germicicle being 2 to 4% by weight of said composition.

3. A detergent-germicide composition consisting of a quaternary ammonium germicide, an alkali metal car bonate and sodium tripolyphosphate, the ratio of carbonate to polyphosphate being 1 to 27.

4. A detergent-germicicle composition consisting of a quaternary ammonium germicide, an alkali metal carbonate and sodium tetrapolyphosphate, the ratio of car bonate to polyphosphate being 1 to 2-7.

5. A detergent-germicide composition consisting of a quaternary ammonium germicide, an alkali metal carbonate and an alkali metal polyphosphate taken from the class consisting of alkali metal triphosphates and tetraphosphates, the ratio of carbonate to polyphosphate being 1 to 27, and containing a substantial amount of an inorganic salt having detergent properties.

6. A detergent-germicide composition consisting of a quaternary ammonium germicide, an alkali metal carbonate and an alkali metal polyphosphate taken from the class consisting of alkali metal triphosphates and tetraphosphates, the ratio of carbonate to polyphosphate being 1 to 2-7, and containing 1 to 50% by weight of an inorganic salt having detergent properties.

7. A detergent-germicide composition consisting of a quaternary ammonium germicide, an alkali metal carbonate and an alkali metal polyphosphate taken from the class consisting of alkali metal triphosphates and tetraphosphates, the ratio of carbonate to polyphospnate being 1 to 2-7, and containing a substantial amount of an alkali metal salt taken from the class consisting of phosphate, metasilicate and borate having detergent properties.

8. A detergent-germicide composition consisting of a quaternary ammonium germicide, an alkali metal carbonate and an alkali metal polyphosphate taken from the class consisting of alkali metal triphosphates and tetraphosphates, the ratio of carbonate to poiyphosphate being 1 to 2-7, and containing a substantial amount of a non-ionic Wetting agent.

9. A detergent-germicide composition consisting of a quaternary ammonium germicide, an alkali metal carbonate and an alkali metal polyphosphate taken from the class consisting of alkali metal triphosphates and tetraphosphates, the ratio of carbonate to pelyphosphate being 1 to 27, and containing a substantial amount of a nonionic wetting agent taken from the class consisting of fatty acid esters and ethers of higher polyalcohols and condensation products of higher fatty acids and polyalkylolamines.

References Cited in the file of this patent UNITED STATES PATENTS 2,474,412 Bersworth June 28, 1949 2,515,880 MacMahon July 18, 1950 2,519,747 DuBois Aug. 22, 1950 2,519,841 MacMahon Aug. 22, 1950 2,584,056 Soule Jan. 29, 1952 

2. A DETERGENT-GERMICIDE COMPOSITION CONSISTING OF A QUATERNARY AMMONIUM GERMICIDE, AN ALKALI METAL CARBONATE AND AN ALKALI METAL POLYPHOSPHATE TAKEN FROM THE CLASS CONSISTING OF ALKALI METAL TRIPHOSPHATES AND TETRAPHOSPHATES, THE RADIO OF CARBONATE TO POLYPHOSPHATE BEING 2 TO 2-7, THE AMOUNT OF SAID GERMICIDE BEING 2 TO 4% BY WEIGHT OF SAID COMPOSITION. 